Derivatives of the pyrazolanthrone and process of preparing them



Patented Aug. 12, 1930 KARI. WILKE, 'rnmss, AND OTTO BR HOCHST, GERMANY, ASSIGNORS TO AUNSDORF, 0F FRANKIORT-ON THE- MAIN- GENERAL ANILINE WORKS, INC.,' 013 NEW YORK, N. Y.,' A CORPORATION OF DELAWARE DERIVATIVES or me RYRAZOLA TIIRONE AND PROCESS, OF PREPARING THEM N Drawing. Originalappligation filed(Octobr 10, 1927, Serial N ,225,38 8,.and in Germany Qetober 32,

1926. Divided andthis app lication filed August 12,

Our present invention relates to derivatives of the pyrazolanthrone. and a processjof preparing them. I i

lVe have found that new derivatives of the.

pyrazolanthrone of the following general formula: 1 e.

substituted residue" of the group consisting of the benzene, naphthalene or ,anthraquinone serles, A

R stands for oxygen, v R stands for hydrogen or R and R together stand for are obtainable by treating pyraz'olanthrone or a pyrazolanthrone wherein .the hydrogen atom of the NH-group is substitute by any metal, or their substitution "products in a 7 suitable manner with halogen-substitution products of the group consistingof the benzene, naphthalene= or =anthraquinone series. Among the compounds in question We may mention for instance? l lalogen-benzenes,

nitrohalogen-benzenesf or nitrohalogen-naphthalenes, Ortho-halogen carboxylic acids of.

the benzene-, naphthalene or, anthraquinone series, "1-chloro 2methylanthraquinone or,

the like. The reaction is preferabIycarried out man organiosolyent Withadditionofone of the known agents capable of promoting the splitting ofi? fof halogen hydride and addition of a catalyst,fsuch"as "copper pow i der, copper. saltsQand vanadium salts orlthe like. Incertain'ca 'es thejapplication ofpres sureisrequired; I

V c l wherein X stands for a subst tuted or un- Wlco 101 and Wlter and drled "drous potassiunfacet The new. bodies theiprocess 1929. Serial No. 385,471.

above set forth are of manufacture of dyestufls.

The following examples serve to illustrate our phenylpyrazolanthrone has y the following formula:

It crystallizes from glacialfacetic acid in the form-of beautiful p large yellow crystalline needles which melt at 211 yellow fluorescence.

(2) llparts of pyrazolanthrone, 10 parts great value in the invention but they are notintendedto limit it thereto; the parts being parts by (1) Equal parts of pyrazolanthrone, bro-' The resulting In conic en-n trated SLIlfLlTIC ELCICl the product dissolves with a red colorwvithout any fluorescence, in an" 755 I organic solvent vvlth a more or less ntense of o-bromdbenz oicgacid, lOpartsYoiE aIihya e 0,5 PM Of sorr acetate, 0,1 part of copper poivderare introduced,'while stirring, into 100 parts of amyl alcohol and the mixture is gradually heated to: boiling and kept so for about 12 lilonrs. A 'partj'of.theaproduct separatesin the course of thereaction as a yellow potassium saltan'd another part remains'dissolveclgin the amyl" alcohol as the free base. I In order to ,WQI'k Up the product, itis advantageous to expelthe, amyl l oh by mea sof, te m mmediately "After filtration the amyl alcohol is refluorescence.

from the reaction mixture after having added thereto water and sodium carbonate, then to filter from the dark-yellow solution of the sodium salt any pyrazolanthronc which may have remained undissolved and unattacked and to precipitate the latter by means of a dilute mineral acid. The phenylpyrazolanthrone-ortho-carboxylic acid then precipitates as a yellow flocculent precipitate and, after being dried, forms a yellow powder.

By recrystallization for instance from glacial acetic acid, it can be easily purified and thenmelts at 262 C.265 C. In a dilute solution of sodium Carbonate it readily dissolves even in the cold with a yellow color;

it dissolves in concentrated sulfuric acid to an orange solution with a slightly yellowish The phenylpyrazolanthroneortho-carboxylic acid dissolves in chlorosultonic acld at first to an orange-yellow solution which in a few seconds turns dull brown and finally greenish.

(3) There are treated and subjected to reaction as indicated in Example (2) the following parts of the respective compounds:

22 parts of pyrazolanthrone 16 parts of ortho-chlorobenzoic acid 20 parts of dehydrated potassium acetate .1 partof copper acetate 0,1 part of copper powder.

The derivatives of the pyrazolanthrone obtainable according to Examples (2) and (3) are identical; they have the following formula OOH

Its solution in concentrated sulfuric acid is of an orange color with a slight fluorescence. Its behaviour towards chlorosulfonic acid is quite similar to that of the phenylpyrazolanthrone-ortho-carboxylic acid. It has the following formula:

(5) parts of p razolanthrone, 38 parts of ortho-chlor-nitro enzene, 30 parts of anhydrous potassium carbonate, 2 parts of copper carbonate and a minute quantity of copper powder are introduced together into 400 parts of nitrobenzene, while stirring.

The mixture is slowly heated to a temperature of approximately 200 C. and kept at this temperature until the reaction is comsponds to the following formula:

(4) There are treated and subjected to reaction as indicated in Example (2) the following parts of the respective compounds:

22' parts of pyrazolanthrone 22 parts of 2-chlor-3-naphthoic acid 15 parts of potassium acetate 1 part of copper acetate 6,5 part of copper in y 7 200 parts of amyl alcohol.

moved. The residue is then dissolved in sodium carbonate. By treating this. solution with anacid a light-yellow precipitate is prov duced.fl The dried product is a light-yellow powder which, after recrystallization from glacial acetic acid, melts at 277 C. to 279 C. v

with eifervescence (splitting off of 00;).

(6) 45 parts of pyrazolanthrone, 25 parts of alpha-chlor-anthraquinone, 30 parts of potassium carbonate with a small quantity of .a copper salt added thereto are heated for about 12 hours, while stirring, in 400 to 500 parts of nitrobenzene until the solvent begins to boil gently. After cooling, the mass is 'diluted with ethyl alcohol, filtered by suction 1 and washed'with alcohol and hot water. The

N-alphaanthraquinonyl-pyrazolanthrone is left as a yellowish-brown powder, which dissolves in concentrated sulfuric acid with a yellowish-red color.

By addition of alkaline .hydrosulfite a brownish-red vat is obtained from which cotton fiber is dyed very faint yellowish tints. The product corresponds to the formula:

(7) 45 parts of pyrazolanthrone, mixed with 24 parts of 1.5-dichloro-2.4dinitrobenzene, 15 parts of anhydrous potassium car bonate, lpart of copper carbonate and a minute quantity of copper powder, are introduced into 450 parts of. nitrobenzene at 190 C. to 200 C. and stirred therein-for a considerable time. After the resulting mass has been worked up in the manner explained in the foregoing examples, a product free from chlorine is obtained which, as is proved by its analysis and properties, has been formed by the exchange of the two (ll-atoms of the dichlordinitrobenzene for the .pyrazolanthrone residue. The product forms a yellow powder which dissolves in concentrated sulfuric acid with a yellow color. Inorganic solvents of high boiling point, such as nitro-' benzene, it is only soluble with great difliculty. The new productcorresponds to the following formula:

(8) Equalpartsofpyrazolanthrone and .alpha-brom-naphthalene areheated in about 8 times the quantity of nitrobenzene to which the calculated quantity of anhydrous potassium carbonate and a minute quantity of copper. carbonate has been added, until, the

reaction is complete. I The massis allowed to Q cool, then filtered with suction, washed free I from nitrobenzene with alcohol andfor reunaltered.

moving anyinorganic salts with dilute hydrochloric acid and finally with hot-water. There is left a yellowish-brown residue which constitutes the N-1'-naphthylpyrazolanthrone of the following formula? filtrate as a yellow precipitate. It dissolves in'dilute alkalies with ayellow color, in concentrated sulfuric acid with a yellow color and in choloro-sulfonic acid also-with a yellow colorwhich, however, in a few seconds changes first to red, then to violet and finally to pure blue color. From this'blu'e solution the product can no longer be precipitated We wish it to be understood that the expression anthraquinone series in the fo1lowmg claims is not intended toinclude products of the "benzanthrone series.

This application is a division of our copending U. S. patent application Ser. No.

225,388 filed on October 10, 1927.

Weclaim:

1. As new products, the derivatives of the pyrazolanthrone of the following formula:

wherein X stands for a substituted or unsubstituted residue of the group consisting of thebenzene, naphthalene or 'anthraquinone series, R foroxygem-R for hydrogen or R and R together stand for N-IL u a Inc 2; As new products, the derivatives of the pyrazolanthrone of the following formula:

wherein X stands for a substituted or unsubstituted benzene-residue, R for oxygen, R- for hydrogen or R and R together stand for l N-N II 3. As new products, the derivatives of the pyrazolanthrone of the following formula Z HQ wherein Z stands for hydrogen, the carboxy group or the nitro group.

' 4. As a new product, phenyl-pyrazolanthrone-ortho-carb0xylic acid which, when recrystallized from glacial acetic acid, forms a yellow powder melting at from 262 C. to 265 C. and dissolving in concentrated sulfuric acid to an orange solution of a slightly yellowish fluorescence. V

In testimony whereof, we afiix our signatures.

KARL WILKE. KARL THIESS. OTTO BRAUNSDORF. 

